CN103993315B - A kind of CaP-TiO 2the preparation technology of compound bio film - Google Patents
A kind of CaP-TiO 2the preparation technology of compound bio film Download PDFInfo
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- CN103993315B CN103993315B CN201410246773.8A CN201410246773A CN103993315B CN 103993315 B CN103993315 B CN 103993315B CN 201410246773 A CN201410246773 A CN 201410246773A CN 103993315 B CN103993315 B CN 103993315B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000005516 engineering process Methods 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 title claims abstract description 16
- 238000004544 sputter deposition Methods 0.000 claims abstract description 64
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 27
- 238000007669 thermal treatment Methods 0.000 claims abstract description 18
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 17
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 12
- 229910052786 argon Inorganic materials 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000013077 target material Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000005488 sandblasting Methods 0.000 claims abstract description 4
- 238000005477 sputtering target Methods 0.000 claims abstract description 4
- 239000011247 coating layer Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 230000004071 biological effect Effects 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 15
- 239000000758 substrate Substances 0.000 abstract description 13
- 239000010408 film Substances 0.000 description 139
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 27
- 239000012890 simulated body fluid Substances 0.000 description 22
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- 229910001069 Ti alloy Inorganic materials 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- MWKXCSMICWVRGW-UHFFFAOYSA-N calcium;phosphane Chemical compound P.[Ca] MWKXCSMICWVRGW-UHFFFAOYSA-N 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- -1 argon ion Chemical class 0.000 description 2
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- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a kind of CaP-TiO
2the preparation technology of compound bio film, this kind of technique adopts prepares hydroxyapatite coating layer on the tinsel surface through sandblasting, adopts magnetron sputtering method, at the TiO of preparation
2using hydroxyapatite sprayed target as sputtering target material on film, continue sputtering CaP film, obtain CaP-TiO
2compound bio film, carries out subsequent heat treatment to the laminated film prepared, and adopts argon gas to add the heat-treating atmosphere of water vapor, is incubated l ~ 3h, afterwards furnace cooling under 600 ~ 800 DEG C of thermal treatment temps; Greatly, have good biological activity, preparation technology is easy, cost is low for the laminated film that the present invention obtains and substrate combinating strength, and target is by the restriction of size.
Description
Technical field
The present invention relates to biofilm technical field, particularly a kind of CaP-TiO
2the preparation technology of compound bio film.
Background technology
At present, the method that titanium alloy surface prepares biological coating and film has a variety of, is broadly divided into Physical, electrochemical process, chemical method three major types.Wherein, conventional Physical comprises: plasma spraying, laser melting coating, magnetron sputtering, pulsed laser deposition etc.Magnetic control sputtering system places 100 ~ 1000Gauss strong magnets in the behind of cathode targets, and vacuum chamber is filled with the rare gas element (Ar) of 0.1 ~ 10Pa pressure, as the carrier of geseous discharge.Under High Pressure, Ar atomic ionization becomes argon ion (Ar
+) and electronics, produce plasma glow discharge, electronics flies in the process of matrix in acceleration, be subject to the influence of magnetic field perpendicular to electric field, make electronics produce deflection, be bound in the heating region on target surface, electronics advances along target surface in the mode of cycloid, in moving process constantly and Ar atom collide, ionize out a large amount of Ar
+, with do not have magnetron structure sputtering compared with, ionization level increases sharply 10 ~ 100 times, and therefore in this region, plasma density is very high.After multiple impacts, the energy of electronics reduces gradually, breaks away from the constraint of magnetic line of force, finally drops on matrix, vacuum chamber inwall and target source anode.And Ar
+under high-voltage electric field booster action, give off energy with the shock of target, cause the atomic absorption Ar of target material surface
+kinetic energy and depart from the constraint of former lattice, matrix is flown on the surface in neutral target atom effusion target, and forms film at substrate deposit.
In magnetron sputtering, owing to there being high-energy particle bombardment target, therefore require very high to preparation of target materials, generally can not carry out the sputtering of powder and the not high target of density.At present, the normal hydroxyapatite HA pottery adopted is as the target of preparation Ca-P film, but HA brittleness of ceramics is very large, easily broken when high-energy sputters.The target of current magnetron sputtering mostly is hot pressed sintering and forms, and complex process, cost is higher.
Summary of the invention
The object of this invention is to provide a kind of CaP-TiO
2the preparation technology of compound bio film, this kind preparation technology is simple, cost is low, obtained film performance is good.
For achieving the above object, the technical scheme that the present invention takes is:
A kind of CaP-TiO
2the preparation technology of compound bio film, comprises the steps:
(1) preparation of hydroxyapatite sprayed target: the tinsel selecting suitable dimension as required, by tinsel after cleaning oil removing, sandblasting is carried out under the pressure of 0.15 ~ 0.2MPa, plasma spraying technology is adopted to prepare hydroxyapatite coating layer on its surface afterwards, spray power 35 ~ 45kW, spray distance 90 ~ 120mm, adopt granularity to be 20 ~ 120 μm of hydroxylapatite powders, coat-thickness is 2 ~ 3mm;
(2) magnetron sputtering TiO
2film: the air pressure be evacuated in sputtering chamber reaches 10
-4below Pa, adopt radio-frequency power supply sputter, sputtering power 120 ~ 180W, operating air pressure 0.75 ~ 1.5Pa, base reservoir temperature in the scope of room temperature to 600 DEG C, sputtering time 30 ~ 120min;
(3) in the TiO that step (2) prepares
2film continues sputtering Ca-P film: the spraying target that employing step (1) prepares, as sputtering target material, is evacuated to sputtering chamber internal gas pressure to 10
-4below Pa, adopt radio-frequency power supply sputter, sputtering power 80 ~ 120W, operating air pressure 0.3 ~ 1.5Pa, preferred 0.3-0.75Pa, base reservoir temperature in the scope of room temperature to 600 DEG C, sputtering time 30 ~ 180min;
(4) subsequent heat treatment: carry out subsequent heat treatment to the laminated film that preparation process (3) prepares, adopts argon gas to add the heat-treating atmosphere of water vapor, is incubated l ~ 3h, afterwards furnace cooling, obtains final product under 600 ~ 800 DEG C of thermal treatment temps.
In step (1), described tinsel is preferably copper sheet.
In step (2), preferred sputtering power 150W, operating air pressure 1Pa, base reservoir temperature is room temperature.
In step (3), processing parameter preferred power sputtering 80W, the operating air pressure 0.5Pa of magnetron sputtering C a-P rete, sputtering time 2h, base reservoir temperature are room temperature.
CaP-TiO prepared by the present invention
2the application of compound bio film in artificial skelecton preparation.
The invention has the beneficial effects as follows:
(1) obtained laminated film and substrate combinating strength large: scratch test result shows, Ca-P film and TiO
2the bonding force of transition layer is 23.43N, and TiO
2the existence of transition layer, makes the bonding force of laminated film and matrix be increased to 37.41N;
(2) obtained laminated film after heat treatment has good biological activity;
(3) preparation technology is easy, cost is low, and target is not by the restriction of size, and the smooth densification of spraying target coating, sintering target is not easy to crack relatively, and degree of crystallinity is higher.
Accompanying drawing explanation
Fig. 1 is the surface topography map of hydroxyapatite sprayed target obtained in embodiment 1;
Fig. 2 is the XRD figure spectrum on hydroxyapatite sprayed target surface obtained in embodiment 1;
Fig. 3 a is at glass surface depositing Ti O under 0.75Pa operating air pressure
2the AFM shape appearance figure of film; Fig. 3 b is at glass surface depositing Ti O under 0.75Pa operating air pressure
2the three-dimensional appearance figure of film; Fig. 3 c, Fig. 3 d are respectively under 1.0Pa operating air pressure at glass surface depositing Ti O
2the AFM shape appearance figure of film and three-dimensional appearance figure; Fig. 3 e, Fig. 3 f are respectively under 1.2Pa operating air pressure at glass surface depositing Ti O
2the AFM shape appearance figure of film and three-dimensional appearance figure; Fig. 3 g, Fig. 3 h are respectively under 1.5Pa operating air pressure at glass surface depositing Ti O
2the AFM shape appearance figure of film and three-dimensional appearance figure;
Fig. 4 a, Fig. 4 b deposit TiO under 120W sputtering power
2the surface topography map of film; Fig. 4 c, Fig. 4 d deposit TiO under 150W sputtering power
2the surface topography map of film; Fig. 4 e, Fig. 4 f deposit TiO under 180W sputtering power
2the surface topography map of film;
Fig. 5 deposits TiO under different sputtering power
2the bonding force size (1Pa, 2h) of film;
The bonding force size (0.5Pa, room temperature, 2h) of Ca-P film is deposited under the different sputtering power of Fig. 6;
Fig. 7 a, Fig. 7 b are base reservoir temperature is 100 DEG C of surface topography maps (0.5Pa, 80W, 2h) depositing Ca-P films; Fig. 7 c, Fig. 7 d are base reservoir temperature is 300 DEG C of surface topography maps (0.5Pa, 80W, 2h) depositing Ca-P films; Fig. 7 e, Fig. 7 f are base reservoir temperature is 600 DEG C of surface topography maps (0.5Pa, 80W, 2h) depositing Ca-P films;
Fig. 8 a, Fig. 8 b are the surface topography map (80W, room temperature, 2h) depositing Ca-P film under 0.3Pa operating air pressure; Fig. 8 c, Fig. 8 d are the surface topography map (80W, room temperature, 2h) depositing Ca-P film under 0.5Pa operating air pressure; Fig. 8 e, Fig. 8 f are the surface topography map (80W, room temperature, 2h) depositing Ca-P film under 0.75Pa operating air pressure;
Ca-P film surface cluster-shaped tissue is deposited when Fig. 9 a, Fig. 9 b are operating air pressure 0.5Pa, sputtering power 80W and substrate temperature 600 DEG C;
The cut test result of Figure 10 embodiment 1a and comparative example 1a laminated film;
The cut test result of the laminated film of Figure 11 embodiment 1b and comparative example 1b;
The XRD figure of the laminated film of Figure 12 embodiment 1a;
The XRD figure (80W, room temperature, 2h) of Ca-P film is deposited under Figure 13 different operating air pressure;
After Figure 14 thermal treatment, laminated film embodiment 1b soaks the FTIR after 28 days and schemes in simulated body fluid;
After Figure 15 thermal treatment, laminated film embodiment 1b soaks the XRD figure after 28 days in simulated body fluid;
After Figure 16 a, Figure 16 b thermal treatment, laminated film embodiment 1b soaks the surface topography map after 28 days in simulated body fluid.
Embodiment
Below by specific examples, the present invention will be further elaborated, should be noted that following explanation is only to explain the present invention, not limits its content.
Embodiment 1:
CaP-TiO
2the preparation technology of compound bio film, comprises the steps:
(1) preparation of hydroxyapatite sprayed target: by diameter 76mm, the circular copper sheet of thickness 2mm is after cleaning oil removing, to sandblast alligatoring with Brown Alundum under the pressure of 0.15MPa, utilize SulzerMetco9M air plasma spraying system in its surface preparation coating, spray power 40kW, spray distance 120mm, powder adopts granularity 38.5 ~ 74 μm of hydroxylapatite powders, and preparing coat-thickness is 2mm.
(2) magnetron sputtering method is adopted to prepare TiO
2film: adopt Φ 76 × 4mm that Zhong Li Science and Technology Ltd. of Xiamen City produces, purity is the TiO of 99.99%
2target, is evacuated to the vacuum tightness in sputtering chamber or air pressure to 10
-4below Pa, adopts radio-frequency power supply to sputter, sputtering power 150W, operating air pressure 1Pa, base reservoir temperature room temperature, sputtering time 120min.
(3) in the TiO that step (2) prepares
2film continues sputtering calcium phosphorus film: adopt step (1) prepare spraying target as sputtering target material, be evacuated to the vacuum tightness in sputtering chamber or air pressure to 10
-4below Pa, adopt radio-frequency power supply to sputter, sputtering power 80W, operating air pressure 0.5Pa, substrate Ti alloy (Ti6Al4V), base reservoir temperature room temperature, sputtering time 120min, obtains embodiment 1a.
(4) subsequent heat treatment: the sample of preparation is added in water vapour atmosphere at argon gas and carries out subsequent heat treatment, with the rate of heating of 10 DEG C/min, be heated to 700 DEG C, and be incubated 2h at such a temperature, afterwards furnace cooling, obtain embodiment 1b.
Embodiment 2:
Changing step (2) adopts magnetron sputtering method to prepare TiO
2the operating air pressure of film is respectively 0.75Pa, 1.2Pa, 1.5Pa, and step (1), (3), (4), as embodiment 1, obtain Ca-P/TiO respectively
2compound bio film 2a, 2b, 2c.
Embodiment 3:
Changing step (2) adopts magnetron sputtering method to prepare TiO
2the sputtering power of film is respectively 120W, 180W, and step (1), (3), (4), as embodiment 1, obtain Ca-P/TiO respectively
2compound bio film 3a, 3b.
Embodiment 4:
Change step (3) at TiO
2sputtering power film continuing sputtering calcium phosphorus film is respectively 100W, 120W, and step (1), (2), (4), as embodiment 1, obtain Ca-P/TiO respectively
2compound bio film 4a, 4b.
Embodiment 5:
Change step (3) at TiO
2operating air pressure film continuing sputtering calcium phosphorus film is respectively 0.3Pa, 0.75Pa, and step (1), (2), (4), as embodiment 1, obtain Ca-P/TiO respectively
2compound bio film 5a, 5b.
Embodiment 6:
Change step (3) at TiO
2base reservoir temperature film continuing sputtering calcium phosphorus film is respectively 100 DEG C, 300 DEG C, 600 DEG C, and step (1), (2), (4), as embodiment 1, obtain Ca-P/TiO respectively
2compound bio film 6a, 6b, 6c.
Embodiment 7:
Change step (3) at TiO
2sputtering time film continuing sputtering calcium phosphorus film is respectively 30min, 60min, 180min, and step (1), (2), (4), as embodiment 1, obtain Ca-P/TiO respectively
2compound bio film 7a, 7b, 7c.
Embodiment 8:
Change step (4) subsequent heat treatment temperature and be respectively 600 DEG C, 800 DEG C, step (1), (2), (3), as embodiment 1, obtain Ca-P/TiO respectively
2compound bio film 8a, 8b.
Comparative example 1:
Adopt the method for cosputtering, adopt TiO simultaneously
2target and employing step (1) prepare spraying target and sputter, and sputtering power is 120W, operating air pressure 0.75Pa, substrate Ti alloy (Ti6Al4V), and base reservoir temperature is 100 DEG C, and sputtering time 60min, obtains comparative example 1a.Comparative example 1a is carried out 700 DEG C of thermal treatments in 2 hours, obtain comparative example 1b.
Performance test:
(1) X-ray diffraction analysis (XRD)
Analyze the phase structure of prepared powder, adopt RigakuD/max type X-ray diffractometer.Test condition is: copper target (Cu-K α), pipe stream 100mA, and pipe pressure 40kV, disperse Road narrows DS=10, the sample of counter is spaced apart 0.02 °, and sweep velocity is 4 °/min, disperses and penetrates Road narrows DS=1 °, sweep limit 10 ~ 80 °.
(2) scanning electron microscope morphology analysis (SEM)
SU-70 Hitachi thermal field emission scanning electron microscope is adopted to carry out surface topography and composition analysis to film.SU-70 thermal field emission scanning electron microscope secondary electron image resolving power: 1.0nm (15kV.WD=4.0mm), 1.6nm (1kV.WD=1.5mm, deceleration mode), 2.5nm (1kV.WD=1.5mm).Magnification: low magnification pattern 20-2000X; High-amplification-factor pattern 100-800000X.Acceleration voltage 0.5 ~ 30kV (mode standard), landing voltage 0.1 ~ 2.0kV (deceleration mode).
(3) atomic force microscope morphology analysis (AFM)
NanoScopeDimension3100 type AFM is adopted to carry out Analysis of Surface Topography to film, can viewing film Crystallite Sizes On The Surface and roughness.
(4) bonding strength test
Adopt the WS-2004 type scratching instrument testing film of Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences's development and the bonding strength of matrix.Scratching instrument method of masurement adopts diamond scriber in positive pressure that is constant or that increase continuously, delineates film surface under certain speed, until destroy, using the critical load Lc of correspondence as the tolerance of film and substrate combinating strength.Diamond cone angle 120 °, radius-of-curvature 0.2mm, adopts continuous loading regime in experimentation, cut speed is 2mm/min, and loading velocity is 25N/min, and loading range is 50N, and operation scheme is frictional force.
(5) film thickness test
In the process preparing film, covering part matrix obtains step, adopts XP-2 type step instrument measure step place thus obtain film thickness.
(6) effects of ion concentration determination
Ca measured by the AA370MC type atomic absorption spectrophotometer using Shanghai Precision Scientific Apparatus Co., Ltd to manufacture
2+absorbancy.Absorbancy is larger, shows Ca in solution
2+concentration is larger.
(7) Infrared spectroscopy (FT-IR)
Adopt specular reflection method on NICOLETAvatar370 type Fourier transformation infrared spectrometer, carry out the Infrared spectroscopy of film.The resolving power of instrument is 4cm
-1, scanning times is 32, and sweep limit is 4000 ~ 400cm
-1.OH in infrared spectra reflection sample
-and PO
4 3-deng the information of group characteristic sum crystalline structure.The analytical results of this testing method and XRD combines, can the phase composite of more clearly judgement sample.
(8) biological activity test
Biological activity evaluates an important indicator of biomaterial performance, and it refers to the binding ability between bio-medical material and osseous tissue.The method can tested by external activity carrys out the biological activity of evaluating material, external activity experiment is that sample is immersed in simulated body fluid (Simulatedbodyfluid, SBF) in, through solubility behavior and the depositing behavior of certain hour post analysis sample surfaces ion.The SBF-K9 simulated body fluid prepared by people such as Kokubo is current Application comparison simulated body fluid widely, as shown in table 1, and the ionic concn of this simulated body fluid and human plasma are very close.Adopt pure reagent NaCl, KCl, NaHCO
3, MgCl
26H
2o, K
2hPO
43H
2o, Na
2sO
4, CaCl
2prepare simulated body fluid, utilize (CH
2oH)
3cNH
2pH value to 7.25 is regulated with the HCl of 1mol/L.Table 2 is reagent quality and the addition sequence of preparing 1L simulated body fluid with deionized water.In biofilm immersion test, take simulated body fluid by V
sBFthe ratio of/SA=10cm, wherein SA is the total surface area of sample.The film that will soak is inserted after in the plastic jar that simulated body fluid is housed, and puts into HSS-1 (B) type thermostatic bath and keeps 36.5 DEG C of constant temperature, change once new simulated body fluid every three days.Soak 30 ~ 40min with deionized water again after being taken out by sample, then dry.Soak whether rear film is surperficial has the hydroxyapatite containing carbonate to generate the biological activity judging laminated film by detecting.
The ionic concn contrast (10 of table 1 human plasma and SBF-K9 simulated body fluid
-3mol/L)
Table 2 prepares 1L simulated body fluid (SBF) preparation order and required reagent
Test result:
(1) hydroxyapatite sprayed target surface topography:
The smooth densification of hydroxyapatite sprayed target coating that the present invention obtains, surface topography is shown in Fig. 1; Fig. 2 is the XRD figure spectrum on spraying target surface, as seen from the figure: the obvious degree of crystallinity of the corresponding diffraction peak of HA meets the requirement as target completely.
(2) operating air pressure is to depositing Ti O
2the impact of film surface appearance:
Fig. 3 a-Fig. 3 h is be matrix with glass in the embodiment of the present invention 2, and sputtering power is 150W, under the condition of sputtering time 2h, changes AFM pattern and the three-dimensional appearance figure of the deposition of titania film that operating air pressure obtains.Table 3 is the size of corresponding A FM picture roughness of film, composition graphs 3a to Fig. 3 h and table 3 can find, the Changing Pattern of film matrix deposition of titania film is similar to the sem analysis result of titanium alloy surface deposit film, when air pressure is 0.75Pa, film particles is larger, and skewness, therefore roughness is maximum.Along with the increase of operating air pressure, film surface density increases.When air pressure increases to 1.2Pa by 1Pa, sputtering particle and argon ion collide and increase, and during arrival matrix, energy reduces, and deposited particles mobility reduces, and macrobead is evenly distributed on matrix surface, causes Film roughness to increase again.When operating air pressure increases to 1.5Pa, colliding to increase causes deposited particles to diminish, more easily insert rete space, thus make rete seem comparatively smooth, roughness of film reduces, but the scattering probability meanwhile between sputtering particle and argon gas starts to become large, has therefore occurred a small amount of island structure.
Table 3 different operating air pressure lower-glass surface deposition TiO
2the roughness (150W, 2h) of film
(3) sputtering power is to depositing Ti O
2the impact of film surface appearance and film bonding force
Fig. 4 (a), (b) are for the embodiment of the present invention 3 is at operating air pressure 1Pa, the surface topography of film is prepared during sputtering power 120W, with under Fig. 4 (c), (d) identical operating air pressure, when power is 150W, surface topography is compared, film surface is coarse, and particle is obvious.The surface topography that Fig. 4 (e), (f) are deposit film during sputtering power 180W, deposited particles diameter becomes rapidly large as seen from the figure.By relatively finding, along with the increase of power, surface particles is in trend of growing up rapidly again after first reduction.
Fig. 5 is operating air pressure is 1Pa, deposits TiO under different capacity
2the bonding force size of film, TiO as seen from the figure
2film bonding force is along with the increase of power is in first increasing the trend reduced afterwards.When power is 120W, sputtering particle energy is relatively little, and when it deposits on matrix, particle is comparatively large and diffusion energy is lower, and bonding force is less.When power increases 150W, the less and energy of particle improves, thus is conducive to the atomic diffusion of matrix and film, bonding strength increase.But along with power continues to increase, a large amount of high energy particle pours into titanium alloy surface fast, finally causes internal stress to increase, and bonding force declines.
(4) sputtering power is on the impact of bonding force between Ca-P film and matrix:
Fig. 6 is that the embodiment of the present invention 4 changes at TiO
2film continues the sputtering power of sputtering calcium phosphorus film, the change curve of bonding force and sputtering power between the Ca-P film obtained and matrix, reflect the bonding force of film and matrix along with the increase of power is in the trend reduced.Because sputtering power is excessive, during deposition, make substrate temperature increase, thus produce thermal stresses, cause the bonding force of matrix and film to decline.In addition, along with power increases, a large amount of deposited particles pours into titanium alloy surface fast, does not have time enough fully travelling diffusion on its surface, and occurs promptly assembling, growing, thus stress in thin films is increased, finally cause film bonding force to decline.If but power is too small, is difficult to reach sputtering threshold value, then there will be the phenomenon of build-up of luminance shakiness.
(5) base reservoir temperature is to Ca-P/TiO
2the impact of compound bio film surface appearance:
Fig. 7 (a), (b) for the embodiment of the present invention 6 be 80W at sputtering power, operating air pressure is 0.5Pa, when base reservoir temperature is 100 DEG C, the surface topography of deposition Ca-P film, Fig. 8 (c), d () is same sputtering condition, when substrate temperature is room temperature, the surface topography of deposition Ca-P film, can be found by contrast: raise with substrate temperature, film density improves, when substrate temperature is 100 DEG C, film surface is smooth, even particle distribution, when substrate temperature is 300 DEG C, particle has the trend of growing up, obvious boundary is there is between particle, see Fig. 7 (c), (d), when substrate temperature is 600 DEG C, film surface becomes coarse, particle is more obvious, see Fig. 7 (e), (f), local has large elementide to be formed (as Fig. 9 a, shown in 9b).
(6) operating air pressure is to Ca-P/TiO
2the impact of compound bio film surface appearance:
Fig. 8 a-Fig. 8 f is in the embodiment of the present invention 5, and sputtering power is 80W, sputtering time 2h, and base reservoir temperature is under the condition of room temperature, changes the Ca-P/TiO that operating air pressure obtains
2compound bio film surface appearance figure.
(7) cut test result:
Figure 10 is the cut test result of embodiment of the present invention 1a and comparative example 1a laminated film.Can find out that embodiments of the invention 1a is obvious two flex points, correspond respectively to Ca-P film and TiO
2the bonding force of transition layer, and TiO
2the bonding force of transition layer and matrix.Ca-P film and TiO
2the bonding force of transition layer is 24.4N, and TiO in laminated film
2the bonding force of transition layer and matrix is 34.3N.Only have a flex point in the test result of comparative example 1a, bonding force is 21.2, lower than Ca-P film and TiO in laminated film of the present invention
2the bonding force of transition layer, farther lower than TiO
2the bonding force of transition layer and matrix.
Figure 11 is the cut test result of the laminated film of after heat treatment embodiment 1b and comparative example 1b.Can find out, Ca-P/TiO prepared by after heat treatment the present invention
2still up to 29N, and compared with the Figure 10 before thermal treatment, only having there is a flex point in the bonding force of laminated film embodiment 1b, illustrates that thermal treatment facilitates the inter-level diffusion of laminated film, each rete is combined closely.And the bonding force of comparative example 1b is only 17N, the 21.2N before thermal treatment compares and declines obviously.Visible, Ca-P/TiO of the present invention after thermal treatment
2compound bio film is with the obvious advantage in bonding force.
(8) biological activity test result:
Figure 12 is the Ca-P/TiO that embodiment of the present invention 1a prepares
2the XRD figure of laminated film, can find out that film still only has the diffraction peak of matrix, film is non-crystalline state, but compared with the diffracting spectrum (Figure 13) of magnetron sputtering C a-P film, can find out, in Figure 12, the diffraction peak of matrix obviously dies down, and therefore can judge Ca-P/TiO
2the thickness of laminated film comparatively Ca-P film increases to some extent, but still in non-crystalline state, and there is the cluster tissue of scattered distribution in film surface, if by its implant into body, degradation speed can be caused too fast, thus being unfavorable for the combination with osseous tissue, biological activity, by undesirable, therefore needs to carry out certain subsequent disposal to improve its biological property.
Will at Ar+H
2laminated film after the lower 700 DEG C of thermal treatment 2h of O atmosphere is soaked in SBF, detects its weave construction after 28 days, the biological activity of laminated film after observation thermal treatment.Figure 14 is that after thermal treatment, laminated film embodiment 1b soaks the FTIR after 28 days and schemes in simulated body fluid.1088.47cm is positioned in figure
-1, 1036.43cm
-1and 604.59cm
-1, 569.98cm
-1absorption peak respectively corresponding PO
4 3-the asymmetric stretch of ion and flexural vibration, be positioned at 488.36cm
-1the corresponding PO of absorption peak
4 3-the symmetrical stretching vibration of ion, these are all hydroxyapatite PO
4 3-characteristic peak.1629cm
-1neighbouring peak is the absorption peak of water, 1538.73cm
-1, 803.17cm
-1neighbouring peak is CO
3 2-absorption peak.Figure 15 is that after thermal treatment, laminated film embodiment 1b soaks the XRD figure after 28 days in simulated body fluid, can illustrate in conjunction with infrared spectrogram: in simulated body fluid, soak the surperficial phosphatic rock defining one deck and contain carbonate of rear film, i.e. osteoid apatite, illustrates that the laminated film after thermal treatment has good biological activity.Figure 16 is that after thermal treatment, laminated film embodiment 1b soaks the surface topography after 28 days in simulated body fluid, as can be seen from the figure surface is obviously covered by newly-generated osteoid apatite, and the diffraction peak of XRD analysis result display phosphatic rock is higher than simple HA film.Laminated film biological activity is not only significantly better than before thermal treatment, and compared with the HA film obtained under same heat-treat condition, biological activity is also more outstanding, and this is HA Film Fractionation and TiO mainly
2the coefficient result of transition layer surface active.Illustrate that laminated film is through Overheating Treatment, the requirement of mechanical property can not only be met, and also obtain better biological activity.
Ca-P/TiO prepared by the present invention
2laminated film has good biological activity, can be applicable to the preparation of artificial skelecton.
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (7)
1. a CaP-TiO
2the preparation technology of compound bio film, is characterized in that, comprises the steps:
(1) preparation of hydroxyapatite sprayed target: prepare hydroxyapatite coating layer on the tinsel surface through sandblasting, spray power 35 ~ 45kW, spray distance 90 ~ 120mm, adopt granularity to be 20 ~ 120 μm of hydroxylapatite powders, coat-thickness is 2 ~ 3mm;
(2) magnetron sputtering TiO
2film: the air pressure be evacuated in sputtering chamber reaches 10
-4below Pa, adopt radio-frequency power supply sputter, sputtering power 120 ~ 180W, operating air pressure 0.75 ~ 1.5Pa, base reservoir temperature in the scope of room temperature to 600 DEG C, sputtering time 30 ~ 120min;
(3) in the TiO that step (2) prepares
2film continues sputtering CaP film: the spraying target that employing step (1) prepares, as sputtering target material, is evacuated to sputtering chamber internal gas pressure to 10
-4below Pa, adopt radio-frequency power supply sputter, sputtering power 80 ~ 120W, operating air pressure 0.3 ~ 1.5Pa, base reservoir temperature in the scope of room temperature to 600 DEG C, sputtering time 30 ~ 180min;
(4) subsequent heat treatment: carry out subsequent heat treatment to the laminated film that preparation process (3) prepares, adopts argon gas to add the heat-treating atmosphere of water vapor, is incubated l ~ 3h, afterwards furnace cooling under 600 ~ 800 DEG C of thermal treatment temps.
2. CaP-TiO as claimed in claim 1
2the preparation technology of compound bio film, is characterized in that, in step (1), after first tinsel being carried out cleaning oil removing, then under the pressure of 0.15 ~ 0.2MPa, carries out sandblasting.
3. CaP-TiO as claimed in claim 1
2the preparation technology of compound bio film, is characterized in that, in step (1), described tinsel is copper sheet.
4. CaP-TiO as claimed in claim 1
2the preparation technology of compound bio film, is characterized in that, in step (2), and described sputtered with Ti O
2the sputtering power of film is 150W, operating air pressure is 1Pa, and base reservoir temperature is room temperature.
5. CaP-TiO as claimed in claim 1
2the preparation technology of compound bio film, is characterized in that, the sputtering power of the magnetron sputtering C aP film described in step (3) is 80W, operating air pressure is 0.5Pa, sputtering time 2h, base reservoir temperature are room temperature.
6. CaP-TiO prepared by the preparation technology as described in any one of Claims 1-4
2compound bio film.
7. CaP-TiO according to claim 6
2the application of compound bio film in artificial skelecton preparation.
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|---|---|---|---|---|
| US6419708B1 (en) * | 1997-04-30 | 2002-07-16 | Nobel Biocare Ab | Calcium-phosphate coated implant element |
| CN1736493A (en) * | 2005-08-11 | 2006-02-22 | 上海交通大学 | Method for preparing TiO2-HA biological medical nanometer structured film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6419708B1 (en) * | 1997-04-30 | 2002-07-16 | Nobel Biocare Ab | Calcium-phosphate coated implant element |
| CN1736493A (en) * | 2005-08-11 | 2006-02-22 | 上海交通大学 | Method for preparing TiO2-HA biological medical nanometer structured film |
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| Title |
|---|
| "A review on calcium phosphate coatings produced using a sputtering process-an alternative to plasma spraying";Yunzhi yang et al.;《Biomaterials》;20051231;第26卷;第327-337页 * |
| "The effect of process conditions on the properties of bioactive films prepared by magnetron sputtering";J.Z.Shi et al.;《Vacuum》;20091231;第83卷;第249-256页 * |
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